Effect of weak interfacial interaction between poly(butylene succinate) and microcrystalline cellulose on its crystallization behavior based on crystallization kinetics
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摘要: 为了研究高含量刚性粒子存在下的成核作用和复合材料弱界面相互作用对聚丁二酸丁二醇酯(PBS)结晶行为的影响，采用熔融共混法制备了微晶纤维素(MCC)含量为5wt%~25wt%的PBS/MCC复合材料，利用差示扫描量热仪对PBS/MCC复合单丝的熔融行为和非等温结晶动力学进行了表征和分析，并使用由Jeziorny模型修改的Avrami方法和由Vyazovkin修改的Friedman等转化率方法研究了PBS的结晶行为和结晶机制。结晶动力学研究表明：MCC可以作为有效的成核剂显著提高PBS的结晶温度和结晶速率，促进PBS晶体的生长，且不会改变PBS的成核机制和晶体生长几何形状，但PBS/MCC弱界面相互作用会明显抑制PBS自身成核能力， PBS结晶度从34.8%降低至28.8%。本文结果对研究高含量刚性粒子存在下的弱界面相互作用对PBS结晶行为的影响具有一定的指导意义。Abstract: To study the impact of nucleation effect and weak interface interaction of composite materials in the presence of high content of rigid particles on the non-isothermal crystallization behavior of poly(butylene succinate) (PBS), PBS/MCC composites with microcrystalline cellulose (MCC) content of 5wt%-25wt% were prepared by melt blending. The melting behavior and non-isothermal crystallization kinetics of PBS were characterized by differential scanning calorimetry. The crystallization behavior and mechanism of PBS were analyzed using Avrami method modified by Jeziorny and Friedman's isoconversional method modified by Vyazovkin. Kinetics studies reveal that MCC can act as an efficient nucleating agent to increase the crystallization temperature and crystallization rate of PBS, and promote the growth rate of PBS crystals without changing the nucleation mechanism and crystal growth of PBS, but the weak interface interaction between PBS and MCC will significantly inhibit the nucleation ability of PBS and reduce its crystallinity which reduced from 34.8% to 28.8%. The results of this study have certain guiding significance for studying the influence of weak interface interactions on the crystallization behavior of PBS in the presence of high content rigid particles.
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图 1 不同MCC含量下PBS的升温曲线(a)和降温曲线(b)
Figure 1. Heating curves (a) and cooling curves (b) of PBS with different MCC contents
图 2 不同MCC含量下PBS的相对结晶度Xt与结晶温度(a)和结晶时间(b)的关系
Figure 2. Relationship between relative crystallinity Xt and crystallization temperature (a) and crystallization time (b) of PBS with different MCC contents
图 4 ln(dX/dt)X,i对应–TX,i–1的Friedman曲线
Figure 4. Friedman curves of ln(dX/dt)X,i corresponding to –TX,i–1
图 5 不同MCC含量下PBS的球晶生长状态
Figure 5. Spherical growth state of PBS with different MCC contents
图 6 PBS的结晶过程示意图：(a) 纯PBS；(b) PBS/MCC复合材料
Figure 6. Crystallization mechanism of PBS: (a) Pure PBS; (b) PBS/MCC composite materials
表 1 聚丁二酸丁二醇酯/微晶纤维素(PBS/MCC)复合材料的组成
Table 1. Composition of poly(butylene succinate)/microcrystalline cellulose (PBS/MCC) composite materials
Sample PBS/wt% MCC/wt% PBS 100 0 P-M5 95 5 P-M15 85 15 P-M25 75 25 
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表 2 不同MCC含量下PBS的熔融和结晶特征参数
Table 2. Melting and crystallization characteristic parameters of PBS with different MCC contents
Sample Tm/℃ Tc/℃ ∆Hm/(J·g−1) χc/% ∆Hc/(J·g−1) χc,Tc/% PBS 114.5 77.0 69.5 34.8 59.5 53.8 P-M5 114.2 77.2 62.3 32.8 54.0 51.4 P-M15 114.3 77.4 53.6 31.5 47.4 50.5 P-M25 113.9 79.3 43.2 28.8 41.7 50.3 Notes: Tm—Melting point; Tc—Crystallization temperature; ∆Hm—Melting enthalpy; χc—Crystallinity; ∆Hc—Crystallization enthalpy; χc,Tc—Absolute crystallinity.
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表 3 不同MCC含量下PBS的Avrami和Jeziorny参数
Table 3. Avrami and Jeziorny parameters of PBS with different MCC contents
Sample n Zt Zc t1/2/min PBS 6.4 0.05 0.74 1.50 P-M5 6.3 0.09 0.79 1.38 P-M15 6.4 0.14 0.82 1.28 P-M25 6.2 0.27 0.88 1.16 Notes: n—Avrami index; Zt—Rate constant; Zc—Corrected rate constant; t1/2—The half crystallization time.
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表 4 不同MCC含量下PBS的结晶活化能
Table 4. Crystallization activation energies of PBS with different MCC contents
Xt EX/(kJ·mol–1) PBS P-M5 P-M15 P-M25 0.1 −143.8 −117.8 −130.5 −135.3 0.3 −123.7 −103.5 −122.2 −125.9 0.5 −110.5 −95.4 −111.0 −113.7 0.7 −96.5 −84.2 −95.4 −97.0 0.9 −74.5 −60.5 −69.2 −66.9 Notes: Xt—Relative crystallinity; EX—Crystallization activation energy.
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